Oxidation hair dyes containing 3-aminophenol derivatives, and novel 3-aminophenol derivatives

ABSTRACT

The object of the present patent application are agents for dyeing keratin fibers based on a developer-coupler combination and characterized in that they contain at least one 3-aminophenol derivative of formula (I) or a physiologically compatible, water-soluble salt thereof 
                         
wherein
     R1 denotes a group of the formula   
     
       
         
         
             
             
         
       
         
          or a group of the formula 
       
    
     
       
         
         
             
             
         
       
         
          as well as novel 3-aminophenol derivatives.

The present invention relates to agents for oxidative dyeing of keratinfibers, particularly human hair, based on a developer/couplercombination containing as the coupler a 3-aminophenol derivativesubstituted in the 6-position, as well as novel 3-aminophenolderivatives substituted in the 6-position.

Oxidation dyes have attained substantial importance in the field ofkeratin fiber dyeing and particularly hair dyeing. The color isgenerated by reaction of certain developers with certain couplers in thepresence of an appropriate oxidant. The developers used for this purposeare, in particular, 2,5-diaminotoluene, 2,5-diaminophenylethyl alcohol,p-aminophenol, 1,4-diaminobenzene and4,5-diamino-1-(2-hydroxyethyl)pyrazole, whereas suitable couplers are,for example, resorcinol, 2-methylresorcinol, 1-naphthol, 3-aminophenol,m-phenylenediamine, 2-amino-4-(2′-hydroxyethyl)aminoanisole,1,3-diamino-4-(2′-hydroxyethoxy)benzene and 2,4-diamino-5-fluorotoluene.

In addition to being able to produce colors of the desired intensity,oxidation dyes used for dyeing human hair must meet numerous additionalrequirements. For example, such dyes must be unobjectionable from atoxicological and dermatological standpoint, and the hair colorationsobtained must be highly resistant to light, permanent waving, acids andrubbing. In any case, however, in the absence of exposure to light,rubbing and chemical agents such colorations must remain stable for aperiod of at least 4 to 6 weeks. Moreover, it must be possible, by acombination of suitable developers and couplers, to produce a wide rangeof different color shades.

Although many couplers are already known, with the currently knowncolorants it is not possible to meet the requirements placed on acolorant in every respect. Hence, a need continues to exist for novelcouplers that will meet the aforesaid requirements to an especially highdegree.

We have now found that certain 3-aminophenol derivatives of generalformula (I) meet the requirements placed on couplers to an especiallyhigh degree and with known developers give intense and unusuallylight-fast and wash-fast color shades.

Hence, the object of the present invention is an agent for dyeingkeratin fibers, for example wool, furs, feathers or hair, particularlyhuman hair, said agent being based on a developer-coupler combinationand characterized in that it contains at least one 3-aminophenolderivative of formula (I) or a physiologically compatible, water-solublesalt thereof.

wherein R1 denotes a group of formula (II) or (If)

wherein R2, R3, R4, R5 and R6 independently of each other denotehydrogen, a halogen atom (F, Cl, Br, I), a cyano group, a hydroxylgroup, a C₁–C₄-alkoxy group, a phenoxy group, a C₁–C₄-hydroxyalkoxygroup, a C₁–C₆-alkyl group, a phenyl group, a C₁–C₄-alkyl thioethergroup, a mercapto group, a nitro group, an amino group, aC₁–C₄-alkylamino group, a hydroxy(C₂–C₄)alkylamino group, adi(C₁–C₄)alkylamino group, a di[hydroxy(C₂–C₄)alkyl]amino group, a[dihydroxy(C₃–C₄)alkyl]amino group, a[hydroxy(C₂–C₄)alkyl]-(C₁–C₄)-alkylamino group, a trifluoromethyl group,a —C(O)H group, a —C(O)CH₃ group, a —C(O)CF₃ group, a —Si(CH₃)₃ group, a(C₁–C₄)-hydroxyalkyl group, a (C₂–C₄)-dihydroxyalkyl group, a(C₁–C₄)-aminoalkyl group or a (C₁–C₄)-cyanoalkyl group, or two adjacentR2 to R6 groups form an —O—CH₂—O— bridge;

-   X₁, X₂, X₃, X₄ and X₅ independently of each other denote nitrogen or    a C—R7 group, C—R8 group, C—R9 group, C—R10 group or C—R11 group,    provided that at least one and at the most three of the X₁ to X₅    groups denote nitrogen; and-   R7, R8, R9, R10 and R11 independently of each other denote hydrogen,    a halogen atom (F, Cl, Br, I), a cyano group, a (C₁–C₆)-alkyl group,    a (C₁–C₄)-alkyl thioether group, a mercapto group, a nitro group, an    amino group. a (C₁–C₄)-alkylamino group, a di(C₁–C₄)alkylamino    group, a trifluoromethyl group, a —C(O)H group, a —C(O)CH₃ group, a    —C(O)CF₃ group, a —Si(CH₃)₃ group, a —C(O)—NH₂ group, a    (C₁–C₄)-hydroxyalkyl group or a (C₂–C₄)-dihydroxyalkyl group.

Compounds of formula (1) are, for example:

4-amino-[1,1′-biphenyl]-2-ol, 4-amino-4′-methyl-[1,1′-biphenyl]-2-ol,4-amino-3′-methyl-[1,1′-biphenyl]-2-ol,4-amino-2′-methyl-[1,1′-biphenyl]-2-ol,4-amino-2′,3′-dimethyl-[1,1′-biphenyl]-2-ol,4-amino-2′,4′-dimethyl-[1,1′-biphenyl]-2-ol,4-amino-2′,5′-dimethyl-[1,1′-biphenyl]-2-ol,4-amino-2′,6′-dimethyl-[1,1′-biphenyl]-2-ol,4-amino-3′,4′-dimethyl-[1,1′-biphenyl]-2-ol,4-amino-3′,5′-dimethyl-[1,1′-biphenyl]-2-ol,4-amino-3′,6′-dimethyl-[1,1′-biphenyl]-2-ol,4-amino-2′,4′,5′-trimethyl-[1,1′-biphenyl]-2-ol,4-amino-2′,4′,6′-trimethyl-[1,1′-biphenyl]-2-ol,4-amino-2′,3′,4′-trimethyl-[1,1′-biphenyl]-2-ol,4-amino-2′,3′,5′-trimethyl-[1,1′-biphenyl]-2-ol,4-amino-2′,3′,6′-trimethyl-[1,1′-biphenyl]-2-ol,4-amino-4′-chloro-[1,1′-biphenyl]-2-ol,4-amino-3′-chloro-[1,1′-biphenyl]-2-ol,4-amino-2′-chloro-[1,1′-biphenyl]-2-ol,4-amino-4′-fluoro-[1,1′-biphenyl]-2-ol,4-amino-3′-fluoro-[1,1′-biphenyl]-2-ol,4-amino-2′-fluoro-[1,1′-biphenyl]-2-ol,4-amino-4′-bromo-[1,1′-biphenyl]-2-ol,4-amino-3′-bromo-[1,1′-biphenyl]-2-ol,4-amino-2′-bromo-[1,1′-biphenyl]-2-ol,4-amino-3′,5′-dichloro-[1,1′-biphenyl]-2-ol,4-amino-3′,5′-difluoro-[1,1′-biphenyl]-2-ol,4-amino-3′-bromo-5′-methyl-[1,1′-biphenyl]-2-ol,4-amino-4′-(trifluoromethyl)-[1,1′-biphenyl]-2-ol,4-amino-3′-(trifluoromethyl)-[1,1′-biphenyl]-2-ol,4-amino-2′-(trifluoromethyl)-[1,1′-biphenyl]-2-ol,4-amino-4′-nitro-[1,1′-biphenyl]-2-ol,4-amino-3′-nitro-[1,1′-biphenyl]-2-ol,4-amino-2′-nitro-[1,1′-biphenyl]-2-ol,4-amino-5′-methyl-3′-nitro-[1,1′-biphenyl]-2-ol,4-amino-4′-methyl-3′-nitro-[1,1′-biphenyl]-2-ol,4-amino-2′-methyl-3′-nitro-[1,1′-biphenyl]-2-ol,4-amino-2′-nitro-4′-(trifluoromethyl)[1,1′-biphenyl]-2-ol,4-amino-3′-nitro-5′-(trifluoromethyl)[1,1′-biphenyl]-2-ol,4-amino-3′-nitro-4′-(trifluoromethyl)[1,1′-biphenyl]-2-ol,4-amino-3′-nitro-2′-(trifluoromethyl)[1,1′-biphenyl]-2-ol,4′-amino-2′-hydroxy-[1,1′-biphenyl]4-carbonitrile,4′-amino-2′-hydroxy-[1,1′-biphenyl]-3-carbonitrile,4-amino-4′-methoxy-[1,1′-biphenyl]-2-ol,4-amino-3′-methoxy-[1,1′-biphenyl]-2-ol,4-amino-2′-methoxy-[1,1′-biphenyl]-2-ol,4-amino-4′-ethoxy-[1,1′-biphenyl]-2-ol,4-amino-3′-ethoxy-[1,1′-biphenyl]-2-ol,4-amino-2′-ethoxy-[1,1′-biphenyl]-2-ol,4-amino-3′,4′-dimethoxy-[1,1′-biphenyl]-2-ol,4-amino-3′,5′-dimethoxy-[1,1′-biphenyl]-2-ol,4-amino-2′,3′-dimethoxy-[1,1′-biphenyl]-2-ol,4-amino-2′,4′-dimethoxy-[1,1′-biphenyl]-2-ol,4-amino-2′,5′-dimethoxy-[1,1′-biphenyl]-2-ol,5-amino-2-(1,3-benzodioxol-5-yl)phenol,4-amino-4′-methoxy-3′-methyl-[1,1′-biphenyl]-2-ol,4-amino-4′-methoxy-2′-nitro-[1,1′-biphenyl]-2-ol,4-amino-4′-methoxy-[1,1′-biphenyl]-2-ol,4-amino-4′-phenoxy-[1,1′-biphenyl]-2-ol,4-amino-4′-methylthio-[1,1′-biphenyl]-2-ol,4-amino-3′-methylthio-[1,1′-biphenyl]-2-ol,4-amino-2′-methylthio-[1,1′-biphenyl]-2-ol,4-amino-[1,1′-biphenyl]-2,4′-diol, 4-amino-[1,1′-biphenyl]-2,3′-diol,4-amino-[1,1′-biphenyl]-2,2′-diol,2,2′,3′-trihydroxy-4-amino-[1,1′-biphenyl],2,2′,4′-trihydroxy-4-amino-[1,1′-biphenyl],2,2′,5′-trihydroxy-4-amino-[1,1′-biphenyl],2,2′,6′-trihydroxy-4-amino-[1,1′-biphenyl],2,3′,4′-trihydroxy-4-amino-[1,1′-biphenyl],2,3′,5′-trihydroxy-4-amino-[1,1′-biphenyl],4-amino-2′-methyl-[1,1′-biphenyl]-2,4′-diol,2′,4-diamino-[1,1′-biphenyl]-2-ol, 3′,4-diamino-[1,1′-biphenyl]-2-ol,4,4′-diamino-[1,1′-biphenyl]-2-ol,4′,4-diamino-[1,1′-biphenyl]-2,2′-diol,3′,4-diamino-[1,1′-biphenyl]-2,2′-ol [sic],3′,4-diamino-[1,1′-biphenyl]-2,4′-ol [sic],3′,4-diamino-[1,1′-biphenyl]-2,5′-ol [sic],3′,4-diamino-[1,1′-biphenyl]-2,6′-ol [sic],2′,3′,4-triamino-[1,1′-biphenyl]-2-ol,2′,4,4′-triamino-[1,1′-biphenyl]-2-ol,2′,4,5′-triamino-[1,1′-biphenyl]-2-ol,2′,4,6′-triamino-[1,1′-biphenyl]-2-ol,3′,4,4′-triamino-[1,1′-biphenyl]-2-ol,3′,4,5′-triamino-[1,1′-biphenyl]-2-ol,1-(4′-amino-2′-hydroxy-1,1′-biphenyl-4-yl)ethanone,4-amino-1,1′:3′,1″-terphenyl-2-ol, 4-amino-1,1′:4′,1″-terphenyl-2-ol,4-amino-4′-(aminomethyl)-[1,1′-biphenyl]-2-ol,4-amino-3′-(aminomethyl)-[1,1′-biphenyl]-2-ol,4-amino-2′-(aminomethyl)-[1,1′-biphenyl]-2-ol,(4′-amino-2′-hydroxy-1,1′-biphenyl-4-yl)acetonitrile,(4′-amino-2′-hydroxy-1,1′-biphenyl-3-yl)acetonitrile,(4′-amino-2′-hydroxy-1,1′-biphenyl-2-yl)acetonitrile,5-amino-2-(4-pyridinyl)phenol, 5-amino-2-(3-pyridinyl)phenol,5-amino-2-(2-pyridinyl)phenol, 5-amino-2-(3-methyl-2-pyridinyl)phenol,5-amino-2-(4-methyl-2-pyridinyl)phenol,5-amino-2-(5-methyl-2-pyridinyl)phenol,5-amino-2-(6-methyl-2-pyridinyl)phenol,5-amino-2-(3-chloro-2-pyridinyl)phenol,5-amino-2-(4-chloro-2-pyridinyl)phenol,5-amino-2-(5-chloro-2-pyridinyl)phenol,5-amino-2-(6-chloro-2-pyridinyl)phenol,5-amino-2-(3-fluoro-2-pyridinyl)phenol,5-amino-2-(4-fluoro-2-pyridinyl)phenol,5-amino-2-(5-fluoro-2-pyridinyl)phenol,5-amino-2-(6-fluoro-2-pyridinyl)phenol,5-amino-2-(3-trifluoromethyl-2-pyridinyl)phenol,5-amino-2-(4-trifluoromethyl-2-pyridinyl)phenol,5-amino-2-(5-trifluoromethyl-2-pyridinyl)phenol,5-amino-2-(6-trifluoromethyl-2-pyridinyl)phenol,5-amino-2-(3-nitro-2-pyridinyl)phenol,5-amino-2-(4-nitro-2-pyridinyl)phenol,5-amino-2-(5-nitro-2-pyridinyl)phenol,5-amino-2-(6-nitro-2-pyridinyl)phenol,5-amino-2-(2-methyl-3-pyridinyl)phenol,5-amino-2-(4-methyl-3-pyridinyl)phenol,5-amino-2-(5-methyl-3-pyridinyl)-phenol,5-amino-2-(6-methyl-3-pyridinyl)phenol,5-amino-2-(2-chloro-3-pyridinyl)phenol,5-amino-2-(4-chloro-3-pyridinyl)phenol,5-amino-2-(5-chloro-3-pyridinyl)phenol,5-amino-2-(6-chloro-3-pyridinyl)phenol,5-amino-2-(2-bromo-3-pyridinyl)phenol,5-amino-2-(4-bromo-3-pyridinyl)phenol,5-amino-2-(5-bromo-3-pyridinyl)phenol,5-amino-2-(6-bromo-3-pyridinyl)phenol,5-amno-2-(2-nitro-3-pyridinyl)phenol,5-amino-2-(4-nitro-3-pyridinyl)phenol,5-amino-2-(5-nitro-3-pyridinyl)phenol,5-amino-2-(6-nitro-3-pyridinyl)phenol, 5-amino-2-(5-pyrimidinyl)phenoland 5-amino-2-(4-pyrimidinyl)phenol, as well as the physiologicallycompatible, water-soluble salts thereof.

Preferred compounds of formula (I) are those wherein;

-   (i) R1 stands for a group of formula (II) with R2 and R6 denoting    hydrogen, or (ii) R1 stands for a group of formula (E) with X₁ and    X₅ denoting C—R7 and C—R11, with R7 and R11 denoting hydrogen.

Particularly preferred are the following compounds of formula (1):

4-amino-3′-methyl-[1,1′-biphenyl]-2-ol,4-amino-4′-methyl-3′-nitro-[1,1′-biphenyl]-2-ol,4-amino-[1,1′-biphenyl]-2,4′-diol, 5-amino-2-(3-pyridinyl)phenol and5-amino-2-(5-pyrimidinyl)phenol as well as the physiologicallycompatible, water-soluble salts thereof.

The compounds of formula (I) can be used as the free bases as well as inthe form of their physiologically compatible salts of inorganic ororganic acids, for example hydrochloric acid, sulfuric acid, phosphoricacid, acetic acid, propionic acid, lactic acid or citric acid.

The 3-aminophenol derivatives of formula (1) are present in the colorantof the invention in a total amount from about 0.005 to 20 weightpercent, an amount from about 0.01 to 5 wt. % and particularly from 0.1to 2.5 weight percent being preferred.

Preferred developers are 1,4-diaminobenzene (p-phenylenediamine),1,4-diamino-2-methylbenzene (p-toluylenediamine),1,4-diamino-2,6-dimethylbenzene, 1,4-diamino-3,5-diethylbenzene,1,4-diamino-2,5-dimethylbenzene, 1,4-diamino-2,3-dimethylbenzene,2-chloro-1,4-diaminobenzene, 1,4-diamino-2-(thiophen-2-yl)benzene,1,4-diamino-2-(thiophen-3-yl)benzene,1,4-diamino-2-(pyridin-3-yl)benzene, 2,5-diaminobiphenyl,1,4-diamino-2-methoxymethylbenzene, 1,4-diamino-2-aminomethylbenzene,1,4-diamino-2-hydroxymethylbenzene,1,4-diamino-2-(2-hydroxyethoxy)benzene,2-[2-(acetylamino)ethoxy]-1,4-diaminobenzene, 4-phenylaminoaniline,4-dimethylaminoaniline, 4-diethylaminoaniline, 4-dipropylaminoaniline,4-[ethyl-(2-hydroxyethyl)amino]aniline,4-[di(2-hydroxyethyl)amino]aniline,4-[di(2-hydroxyethyl)amino]-2-methylaniline,4-[(2-methoxyethyl)amino]aniline, 4-[(3-hydroxypropyl)amino]aniline,4-[(2,3-dihydroxypropyl)amino]aniline,1,4-diamino-2-(1-hydroxyethyl)benzene,1,4-diamino-2-(2-hydroxyethyl)benzene,1,4-diamino-2-(1-methylethyl)benzene,1,3-bis-[(4-aminophenyl)(2-hydroxyethyl)amino]-2-propanol,1,4-bis-[(4-aminophenyl)amino]butane,1,8-bis-(2,5-diaminophenoxy)-3,6-dioxaoctane, 4-aminophenol,4-amino-3-methylphenol, 4-amino-3-(hydroxymethyl)phenol,4-amino-3-fluorophenol, 4-methylaminophenol,4-amino-2-(aminomethyl)phenol, 4-amino-2-(hydroxymethyl)phenol,4-amino-2-fluorophenol, 4-amino-2-[(2-hydroxyethyl)amino]methylphenol,4-amino-2-methylphenol, 4-amino-2-(methoxymethyl)phenol,4-amino-2-(2-hydroxyethyl)phenol, 5-aminosalicylic acid,2,5-diaminopyridine, 2,4,5,6-tetraminopyrimidine,2,5,6-triamino-4-(1H)-pyrimidone,4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole,4,5-diamino-1-(1-methylethyl)-1H-pyrazole,4,5-diamino-1-[(4-methylphenyl)methyl]-1H-pyrazole,1-[(4-chlorophenyl)methyl]-4,5-diamino-1H-pyrazole,4,5-diamino-1-methyl-1H-pyrazole, 2-aminophenol, 2-amino-6-methylphenol,2-amino-5-methylphenol and 1,2,4-trihydroxybenzene.

Moreover, besides the compounds of formula (I) the colorant of theinvention can also contain other known couplers, for exampleN-(3-dimethylaminophenyl)urea, 2,6-diaminopyridine,2-amino-4-[(2-hydroxyethyl)amino]anisole,2,4-diamino-1-fluoro-5-methylbenzene,2,4-diamino-1-methoxy-5-methylbenzene,2,4-diamino-1-ethoxy-5-methylbenzene,2,4-diamino-1-(2-hydroxyethoxy)-5-methylbenzene,2,4-di[(2-hydroxyethyl)amino]-1,5-dimethoxybenzene,2,3-diamino-6-methoxypyridine,3-amino-6-methoxy-2-(methylamino)pyridine,2,6-diamino-3,5-dimethoxypyridine, 3,5-diamino-2,6-dimethoxypyridine,1,3-diaminobenzene, 2,4-diamino-1-(2-hydroxyethoxy)benzene,1,3-diamino-4-(2,3-dihydroxypropoxy)benzene,1,3-diamino-4-(3-hydroxypropoxy)benzene,1,3-diamino-4-(2-methoxyethoxy)benzene,2,4-diamino-1,5-di(2-hydroxyethoxy)-benzene,1-(2-aminoethoxy)-2,4-diamino benzene,2-amino-1-(2-hydroxyethoxy)-4-methylaminobenzene,2,4-diaminophenoxyacetic acid, 3-[di(2-hydroxyethyl)amino]aniline,4-amino-2-di[(2-hydroxyethyl)amino]-1-ethoxybenzene,5-methyl-2-(1-methylethyl)phenol, 3-[(2-hydroxyethyl)amino]aniline,3-[(2-aminoethyl)amino]aniline, 1,3-di(2,4-diaminophenoxy)propane,di(2,4-diaminophenoxy)methane, 1,3-diamino-2,4-dimethoxybenzene,2,6-bis-(2-hydroxyethyl)aminotoluene, 4-hydroxyindole,3-dimethylaminophenol, 3-diethylaminophenol, 5-amino-2-methylphenol,5-amino-4-fluoro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol,5-amino-4-ethoxy-2-methylphenol, 3-amino-2,4-dichlorophenol,5-amino-2,4-dichlorophenol, 3-amino-2-methylphenol,3-amino-2-chloro-6-methylphenol, 3-aminophenol,2-[(3-hydroxyphenyl)amino]acetamide,5-[(2-hydroxyethyl)amino]-4-methoxy-2-methylphenol,5-[(2-hydroxyethyl)amino]-2-methylphenol,3-[(2-hydroxyethyl)amino]phenol, 3-[(2-methoxyethyl)amino]phenol,5-amino-2-ethylphenol, 5-amino-2-methoxyphenol,2-(4-amino-2-hydroxyphenoxy)ethanol,5-[(3-hydroxypropyl)amino]-2-methylphenol,3-[(2,3-dihydroxypropyl)amino]-2-methylphenol,3-[(2-hydroxyethyl)amino]-2-methylphenol, 2-amino-3-hydroxypyridine,2,6-dihydroxy-3,4-dimethylpyridine, 5-amino-4-chloro-2-methylphenol,1-naphthol, 2-methyl-1-naphthol, 1,5-dihydroxynaphthalene,1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene,2,7-dihydroxynaphthalene, 2-methyl-1-naphthol acetate,1,3-dihydroxybenzene, 1-chloro-2,4-dihydroxybenzene,2-chloro-1,3-dihydroxybenzene,1,2-dichloro-3,5-dihydroxy-4-methylbenzene,1,5-dichloro-2,4-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene,3,4-methylenedioxyphenol, 3,4-methylenedioxyaniline,5-[(2-hydroxyethyl)amino]-1,3-benzodioxole,6-bromo-1-hydroxy-3,4-methylenedioxybenzene, 3,4-diaminobenzoic acid,3,4-dihydro-6-hydroxy-1,4(2H)benzoxazine,6-amino-3,4-dihydro-1,4(2H)benzoxazine, 3-methyl-1-phenyl-5-pyrazolone,5,6-dihydroxyindole, 5,6-dihydroxyindoline, 5-hydroxyindole,6-hydroxyindole, 7-hydroxyindole and 2,3-indolinedione.

The couplers and developers can be contained in the colorant of theinvention either individually or in admixture with each other, the totalamount of couplers and developers in the colorant of the invention(based on the total amount of colorant) being from about 0.005 to 20weight percent, preferably from about 0.01 to 5 weight percent andparticularly from 0.1 to 2.5 weight percent, each.

The total amount of the developer-coupler combination contained in thecolorant described herein is preferably from about 0.01 to 20 weightpercent, an amount from about 0.02 to 10 weight percent and particularlyfrom 0.2 to 6 weight percent being especially preferred. In general, thedevelopers and couplers are used in equimolar amounts. However, it isnot disadvantageous if the developers are present in a certain excess ordeficiency with respect to such an amount.

Moreover, the colorant of the invention can also contain additional dyecomponents, for example 6-amino-2-methylphenol and2-amino-5-methylphenol as well as common synthetic or natural directdyes, for example vegetable dyes or synthetic direct dyes from the groupof acid or basic dyes, triphenylmethane dyes, aromatic nitro dyes, azodyes and disperse dyes. The colorants of the invention can contain thesedye components in an amount from about 0.1 to 4 weight percent.

Naturally, the additional couplers and the developers and other dyecomponents, provided they are bases, can also be used in the form oftheir physiologically compatible salts of organic or inorganic acids,for example hydrochloric acid or sulfuric acid, or—if they containaromatic OH— groups—in the form of salts of bases, for example as alkaliphenoxides.

Moreover, if the colorants are used for dyeing hair, they can alsocontain common cosmetic additives, for example antioxidants such asascorbic acid, thioglycolic acid or sodium sulfite, as well as perfumeoils, complexing agents, wetting agents, emulsifiers, thickeners andhair-care agents.

The colorant of the invention can be formulated, for example, as asolution, particularly an aqueous or aqueous-alcoholic solution. Aparticularly preferred formulation, however, is a cream, gel oremulsion. Such a preparation consists of a mixture of dye components andadditives commonly used for such preparations.

Common additives to solutions, creams, emulsions or gels are, forexample, solvents such as water, lower aliphatic alcohols, for exampleethanol, propanol or isopropanol, glycerol or glycols such as1,2-propylene glycol; moreover wetting agents or emulsifiers from theclasses of anionic, cationic, amphoteric or nonionic surface-activesubstances such as, for example, the fatty alcohol sulfates, ethoxylatedfatty alcohol sulfates, alkylsulfonates, alkylbenzenesulfonates,alkyltrimethylammonium salts, alkylbetaines, ethoxylated fatty alcohols,ethoxylated nonylphenols, fatty alkanolamides and ethoxylated fattyesters; furthermore thickeners such as the higher fatty alcohols,starch, cellulose derivatives, petrolatum, paraffin oil and fatty acids;moreover hair-care agents such as cationic resins, lanolin derivatives,cholesterol, pantothenic acid and betaine. The said constituents areused in amounts commonly employed for such purposes, for example thewetting agents and emulsifiers at a concentration from about 0.5 to 30weight percent, the thickeners in an amount from about 0.1 to 30 weightpercent and the hair-care agents at a concentration from about 0.1 to 5weight percent.

Depending on the composition, the colorant of the invention can beweakly acidic, neutral or alkaline. In particular, it has a pH from 6.5to 11.5, the adjustment to a basic value preferably being achieved withammonia. However, amino acids and/or organic amines, for examplemonoethanolamine or triethanolamine, or inorganic bases, for examplesodium hydroxide or potassium hydroxide can also be used. For pHadjustment in the acidic range, an inorganic or organic acid, forexample phosphoric acid, acetic acid, citric acid or tartaric acid, canbe used.

For use in oxidative dyeing of hair, the afore-described colorant ismixed with an oxidant just before use and the resulting mixture isapplied to the hair in an amount sufficient for the hair treatment, ingeneral in an amount from about 60 to 200 grams, depending on thefullness of the hair.

Suitable oxidants for developing the hair coloration are mainly hydrogenperoxide or the compounds of addition thereof to urea, melamine, sodiumborate or sodium carbonate in the form of a 3 to 12%, preferably 6%aqueous solution. Atmospheric oxygen can also be used. If a 6% hydrogenperoxide solution is used as oxidant, the weight ratio of hair colorantto oxidant is from 5:1 to 1:2 and preferably 1:1. Larger amounts ofoxidant are used primarily at higher dye concentrations in the haircolorant or when more pronounced hair bleaching is wanted at the sametime. The mixture is allowed to act on the hair at 15 to 50° C. forabout 10 to 45 minutes, preferably for 30 minutes, after which the hairis rinsed with water and dried. Optionally, following this rinsing thehair is washed with a shampoo and optionally post-rinsed with a weakorganic acid, for example citric acid or tartaric acid. The hair is thendried.

The colorant of the invention containing a 3-aminophenol derivative offormula (I) as coupler gives colorations of excellent color stability,particularly in terms of light fastness, wash fastness and rubbingfastness. As far as the coloring properties are concerned, depending onthe kind and composition of the dye components, the colorant of theinvention provides a wide range of different color shades ranging fromblond to brown, purple, violet, blue and black. Said shades arecharacterized by high color intensity. Furthermore, the very goodcoloring properties of the colorant of the present patent applicationare, in particular, characterized by the fact that this colorant alsomakes it possible to dye gray, chemically not previously damaged hairwith good covering power and without any problems.

The aminophenol derivatives of formula (I) of the invention can beprepared by methods of synthesis known from the literature, for example:

-   a) by tetrakis(triphenylphosphine)palladium(0)-catalyzed coupling of    a suitably substituted 3-aminophenolboric acid derivative of formula    (IV)

-    with a halogen-substituted compound of formula (IIa) or (IIIa)

-    followed by the removal of the protective group needed for the    coupling reaction, or-   b) by tetrakis(triphenylphosphine)palladium(0)-catalyzed coupling of    a halogen-substituted 3-aminophenol derivative of formula (V)

-    with a boric acid derivative of formula (IIb) or (IIIb)

-    followed by the removal of the protective group needed for the    coupling reaction, the groups in formulas (IIa), (IIb), (IIIa),    (IIIb), (IV) and (V) having the following meaning:

Ra denotes a protective group as described, for example, in the chapteron “Protective Groups” in Organic Synthesis, chapter 3, WileyInterscience, 1991;

Rb and Rc independently of each other denote hydrogen or a protectivegroup as described, for example, in the chapter on “Protective Groups”in Organic Synthesis, chapter 7, Wiley Interscience, 1991;

Rd denotes hydrogen or the two Rd groups together with the —O—B—O— groupform an unsubstituted or substituted five-membered or six-memberedcycloaliphatic ring;

Hal denotes F, Cl, Br or I; and

R2, R3, R4, R5 and R6 and X₁, X₂, X₃, X₄ and X₅ have the same meaning asin formulas (II) or (III).

The 3-aminophenol derivatives of formula (I) are readily water-solubleand give colorations of excellent color intensity and color stability,particularly in terms of light fastness, wash fastness and rubbingfastness. Moreover, they have excellent storage stability particularlyas constituents of the afore-described oxidative colorants.

Another object of the present invention are novel 3-aminophenolderivatives of the afore-indicated formula (I) or the physiologicallycompatible, water-soluble salts thereof, provided that (i) R1 is not a2-pyridyl group and (ii) R1 is not a 2-hydroxy-4-aminophenyl group.

The following examples are intended to illustrate the subject matter ofthe invention in greater detail without limiting its scope.

EXAMPLES Examples 1 to 45 Synthesis of 3-aminophenol Derivatives ofGeneral Formula (I)

A. Synthesis of 3-ethoxymethoxyphenylamine

A dispersion of 12 g (274.9 mmol) of sodium hydride (55% in oil) wasadded portionwise at 0° C. to a solution of 20.0 g (183.3 mmol) of3-aminophenol in 450 mL of dried acetonitrile. The mixture was thenallowed to agitate at 0° C. for 3 hours. A solution of 25 g (210.8 mmol)of chloromethyl ethyl ether in 30 mL of acetonitrile was added dropwise,and the mixture was allowed to agitate overnight at room temperature.The reaction mixture was then filtered and the filter cake was washedwith a small amount of acetone. The combined filtrates were evaporated.This gave 32.3 g of 3-ethoxymethoxyphenylamine. The resulting crudeproduct was used in the next step without further purification.

¹H-NMR (300 MHz, DMSO): δ=6.89 (t, 1H, H5); 6.24 (s, 1H, H2); 6.22 (d,1H); 6.16 (d, 1H); 5.14 (s, 2H, NH₂); 5.11 (s, 2H, OCH₂); 3.75 (q, 2H,CH₂); 1.13 (t, 3H, CH₃).

B. Synthesis of tert butyl N-(3-ethoxymethoxyphenyl)carbamate

30 g (180 mmol) of 3-ethoxymethoxyphenylamine from step A and 44.4 g(203 mmol) of ditert.butyl dicarbonate were dissolved in a mixture of140 mL of 2N sodium hydroxide and 200 mL of dichloromethane, and themixture was allowed to agitate for 24 hours at room temperature. Theorganic phase was then separated, washed to a neutral pH with saturatedaqueous sodium chloride solution, dried over MgSO₄, filtered andevaporated. The resulting crude product was purified on silica gel usinghexane/ethyl acetate (8:1).

This gave 18 g (42% of the theoretical based on the amount of3-aminophenol used) of tert.butyl N-(3-ethoxymethoxyphenyl)carbamate asa yellow oil.

¹H-NMR (300 MHz, DMSO): δ=9.33 (s, 1H, NH); 7.20 (s, 1H, H2); 7.14 (t,J=8.0, 1H, H5); 7.05 (d, J=8.0, 1H, H3); 6.63 (d, J=8.0, 1H, H6); 5.17(s, 2H, OCH₂); 3.64 (q, J=7.1, 2H, CH₂); 1.49 (s, 9H, tert.butyl); 1.13(t, J=7.1, 3H, CH₃),

CHN Analysis (C₁₄H₂₁NO₄) % C % H % N Calculated 62.90 7.92 5.24 Found62.60 8.04 4.97C. Synthesis of tert.butyl N-(4-bromo-3-ethoxymethoxyphenyl)carbamate

13.9 g (52 mmol) of tert.butyl N-(3-ethoxymethoxyphenyl)carbamate fromstep B and 10.2 g (57.2 mmol) of N-bromosuccinimide were dissolved undernitrogen in 400 ml, of 1,2-dimethoxyethane, and the solution was allowedto agitate for 3 hours at room temperature. The reaction mixture wasthen poured onto 1000 mL of ice/water and extracted with ethyl acetate.The organic phase was washed with a saturated solution of sodiumchloride, dried over magnesium sulfate and filtered and the filtrate wasevaporated. The resulting crude product was purified on silica gel usinghexane/ethyl acetate (4:1).

This gave 14.4 g (76% of the theoretical) of tert.butylN-(4-bromo-3-ethoxymethoxyphenyl)carbamate as an oil.

¹H-NMR (300 MHz, DMSO): δ=9.50 (s, 1H, NH); 7.45 (d, J=2.0, 1H, H2);7.43 (d, J=8.6, 1H, H5); 7.04 (dd, J=2.0, J=8.6, 1H, H6); 5.24 (s, 2H,OCH₂); 3.70 (q, J=7.1, 2H, CH₂); 1.48 (s, 9H, tert.butyl); 1.16 (t,J=7.1, 3H, CH₃);

CHN Analysis (C₁₄H₂₀BrNO₄) % C % H % N Calculated 48.57 5.82 4.05 Found47.82 5.87 3.77D. Synthesis of tert.butyl[4-(5,5-dimethyl-[1,3,2]dioxaborinan-2-yl)-3-ethoxymethoxyphenyl]carbamate

10 g (28.8 mmol) of tert.butylN-(4-bromo-3-ethoxymethoxyphenyl)carbamate from step C and 13 g (57.6mmol) of 5,5,5′,5′-tetramethyl-2,2′-bi-[1,3,2-dioxaborinane] weredissolved under argon in 260 mL of dioxane. Then, 2.11 g (2.88 mmol) of[1,1′-bis(diphenylphosphino)ferrocene]-dichloropalladium(II) and 8.48 g(86.4 mmol) of potassium acetate were added, and the reaction mixturewas heated at 80° C. for 7 hours. The reaction mixture was then pouredonto 1.6 L of ice/water and extracted with ethyl acetate. The organicphase was washed with saturated aqueous sodium chloride solution, driedover magnesium sulfate and filtered and the filtrate was evaporated. Theresulting crude product was purified on silica gel using hexane/ethylacetate (2:1).

This gave 5.84 g (54% of the theoretical) of tert.butyl[4-(5,5-dimethyl-[1,3,2]dioxaborinan-2-yl)-3-ethoxymethoxyphenyl]carbamate.

1H-NMR (300 MHz, DMSO): δ=9.40 (s, 1H, NH); 7.41 (d, J=8.1, 1H, H5);7.21 (s, 1H, H2); 7.07 (d, J=8.1, 1H, H6); 5.09 (s, 2H, OCH₂); 3.69 (s,4H, BOCH₂); 3.66 (q, J=7.1, 2H, CH₂); 1.48 (s, 9H, tert.butyl); 1.18 (t,3H, CH₃); 0.95 (s, 6H, CH₃).

E. Synthesis of the 3-aminophenols of Formula (1)

0.23 g (0.6 mmol) of tert.butyl[4-(5,5-dimethyl-[1,3,2]dioxaborinan-2-yl)-3-ethoxymethoxyphenyl]carbamatefrom step D and 0.78 mmol of the appropriate bromo derivative weredissolved under argon in 4 mL of 1,2-dimethoxyethane. Then, 0.07 g (0.06mmol) of tetrakis(triphenylphosphine)palladium and 0.8 mL of 2Npotassium carbonate solution were added, and the reaction mixture washeated at 80° C. At the end of the reaction, the reaction mixture waspoured into 15 mL of ethyl acetate, and the organic phase was extractedwith 1N sodium hydroxide solution and then dried with magnesium sulfate.The solvent was distilled off in a rotary evaporator, and the residuewas purified on silica gel using hexane/ethyl acetate.

The product thus obtained was dissolved in 2 mL of ethanol and to it wasadded 1 mL of a 2.9 molar solution of ethanolic hydrochloric acid or of4-molar hydrochloric acid in dioxane. The reaction mixture was thenheated at 55° C. At the end of the reaction, the precipitate wasfiltered off, washed with ethanol (or dioxane) and then dried.

1. 4-Amino-[1,1′-biphenyl]-2-ol hydrochloride

Bromo derivative used: bromobenzene

Yield: 0.041 g (31% of the theoretical)

ESI-MS: 186 [M+H]⁺ (100)

2. 4-Amino-4′-methyl-[1′-biphenyl]-?-ol hydrochloride

Bromo derivative used: 4-bromotoluene

Yield: 0.026 g (18% of the theoretical)

ESI-MS: 200 [M+H]⁺ (100)

3. 4-Amino-3′-methyl-[1,1′-biphenyl]-2-ol hydrochloride

Bromo derivative used: 3-bromotoluene

Yield: 0.048 g (28% of the theoretical)

ESI-MS: 200 [M+H]⁺ (100)

¹-NMR (300 MHz, DMSO): δ=10.15 (s, 1H, OH); 7.31 (s, 1H, H2′); 7.29 (m,3H); 7.13 (d, J=8.1, 1H, H6′); 7.00 (d, J=1.7, 1H, H3); 6.83 (dd, J=1.7,J=8.1, 1H, H5); 3.60 (s, br, 3H, NH₃ ⁺); 2.35 (s, 3H, CH₃).

4. 4-Amino-2′,3′-dimethyl-[1,1′-biphenyl]-2-ol hydrochloride

Bromo derivative used: 3-bromo-o-xylene

Yield: 0.046 g (32% of the theoretical)

ESI-MS: 214 [M+H]⁺ (100)

5. 4-Amino-2′,5′-dimethyl-[1,1′-biphenyl]-2-ol hydrochloride

Bromo derivative used: 2-bromo-p-xylene

Yield: 0.046 g (32% of the theoretical)

ESI-MS: 214 [M+H]⁺ (100)

6. 4-Amino-2′,4′-dimethyl-[1,1′-biphenyl]-ol hydrochloride

Bromo derivative used: 6-bromo-m-xylene

Yield: 0.033 g (17% of the theoretical)

ESI-MS: 214 [M+H]⁺ (100)

7. 4-Amino-3′,4′-dimethyl-[1,1′-biphenyl]-2-ol hydrochloride

Bromo derivative used: 4-bromo-o-xylene

Yield: 0.048 g (32% of the theoretical)

ESI-MS: 214 [M+H]⁺ (100)

8. 4-Amino-3′,5′-dimethyl-[1,1′-biphenyl]-2-ol hydrochloride

Bromo derivative used: 5-bromo-m-xylene

Yield: 0.021 g (13% of the theoretical)

ESI-MS: 214 [M+H]⁺ (100)

9. 4-Amino-2′,4′,5′-trimethyl-[1,1′-biphenyl]-2-ol hydrochloride

Bromo derivative used: 5-bromo-1,2,4-trimethylbenzene

Yield: 0.023 g (14% of the theoretical)

ESI-MS: 228 [M+H]⁺ (100)

10. 4-Amino-4′-chloro-[1,1′-biphenyl]-2-ol hydrochloride,

Bromo derivative used: 1-bromo-4-chlorobenzene

Yield: 0.016 g (10% of the theoretical)

ESI-MS: 220 [M+H]⁺ (100)

11. 4-Amino-4′-chloro-[1′-biphenyl]-2-ol hydrochloride

Bromo derivative used: 1-bromo-3-chlorobenzene

Yield: 0.036 g (23% of the theoretical)

ESI-MS: 220 [M+H]⁺ (100)

12. 4-Amino-2′-chloro-[1,1′-biphenyl]-2-ol hydrochloride

Bromo derivative used: 1-bromo-2-chlorobenzene

Yield: 0.018 g (12% of the theoretical)

ESI-MS: 220 [M+H]⁺ (100)

13. 4-Amino-3′,5′-dichloro-[1,1′-biphenyl]-2-ol hydrochloride

Bromo derivative used: 1-bromo-3,5-dichlorobenzene

Yield: 0.074 g (40% of the theoretical)

ESI-MS: 254 [M+H]⁺ (100)

14. 4-Amino-4′-fluoro-[1,1′-biphenyl]-2-ol hydrochloride

Bromo derivative used: 1-bromo-4-fluorobenzene

Yield: 0.047 g (33% of the theoretical)

ESI-MS: 204 [M+H]⁺ (100)

15. 4-Amino-3′,5′-difluoro-[1,1′-biphenyl]-2-ol hydrochloride

Bromo derivative used: 1-bromo-4-fluorobenzene

Yield: 0.024 g (16% of the theoretical)

ESI-MS: 220 [M−H]⁺ (100)

16. 4-Amino-3′-bromo-5′-methyl-[1,1′-biphenyl]-2-ol hydrochloride

Bromo derivative used: 3,5-dibromotoluene

Yield: 0.022 g (12% of the theoretical)

ESI-MS: 278 [M]⁺ (100)

17. 4-Amino-4′-(trifluoromethyl)-[1,1′-biphenyl]2-ol hydrochloride

Bromo derivative used: 1-bromo-4-(trifluoromethyl)benzene

Yield: 0.017 g (10% of the theoretical)

ESI-MS: 254 [M+H]⁺ (100)

18. 4-Amino-3′-(trifluoromethyl)-[1,1′-biphenyl]-2-ol hydrochloride

Bromo derivative used: 1-bromo-4-(trifluoromethyl)benzene

Yield: 0.017 g (10% of the theoretical)

ESI-MS: 254 [M+H]⁺ (100)

19. 4-Amino-1′-nitro-[1,1′-biphenyl]-2-ol hydrochloride

Bromo derivative used: 1-bromo-3-nitrobenzene

Yield: 0.029 g (18% of the theoretical)

ESI-MS: 253 [M+Na]⁺ (100)

¹H-NMR (300 MHz, DMSO): δ=10.40 (s, br, 1H, OH); 8.16 (d, J=8.0, 1H,H4′); 8.00 (d, J=8.0, 1H, H6′); 7.72 (dd, J=8.0, J=8.0, 1H, H5′); 7.43(d, J=8.2, 1H, H6); 6.92 (s, 1H, H3); 6.78 (d, J=8.2, 1H, H5); 3.46 (s,br, 3H, NH₃ ⁺).

20. 4-Amino-4′-methyl-3′-nitro-[1,1′-biphenyl]-2-ol hydrochloride

Bromo derivative used: 1-bromo-2-nitrotoluene

Yield: 0.082 g (49% of the theoretical)

ESI-MS: 267 [M+Na]⁺ (100)

¹H-NMR (300 MHz, DMSO): δ=10.39 (s, br, 1H, OH); 8.16 (d, J=1.7, 1H,H2′); 7.81 (dd, J=1.7, J=8.0, 1H, H6′); 7.54, (d, J=8.0, 1H, H5′); 7.41(d, J=8.2, 1H, H6); 6.98 (d, J=1.8, 1H, H3); 6.82 (dd, J=1.8, J=8.1, 1H,H5); 3.46 (s, br, 3H, NH₃ ⁺); 2.54 (s, 3H, CH₃).

CHN Analysis: (C₁₃H₁₃N₂O₃HCl) % C % H % N % Cl Calculated 55.62 4.679.98 12.63 Found: 55.10 4.60 9.50 12.2021. 4-Amino-2′-nitro-4′-(trifluoromethyl)[1,1′-biphenyl-2-olhydrochloride

Bromo derivative used: 1-bromo-2-nitro-4-(trifluoromethyl)benzene

Yield: 0.057 g (28% of the theoretical)

ESI-MS: 297 [M−H]⁺ (100)

22. 4′-Amino-2′-hydroxy-[1,1′-biphenyl]-1-carbonitrile hydrochloride

Bromo derivative used: 3-bromobenzonitrile

Yield: 0.036 g (24% of the theoretical)

ESI-MS: 233 [M+Na]⁺ (100)

23. 4-Amino-4′-methoxy-[1,1′-biphenyl]-2-ol hydrochloride

Bromo derivative used: 1-bromo-4-methoxybenzene

Yield: 0.021 g (14% of the theoretical)

ESI-MS: 216 [M+H]⁺ (100)

24. 4-Amino-3′-methoxy-[1,1′-biphenyl]-2-ol hydrochloride

Bromo derivative used: 1-bromo-3-methoxybenzene

Yield: 0.01 g (7% of the theoretical)

ESI-MS: 216 [M+H]⁺ (100)

25. 4-Amino-2′-methoxy-[1,1′-biphenyl]-2-ol hydrochloride

Bromo derivative used: 1-bromo-2-methoxybenzene

Yield: 0.058 g (36% of the theoretical)

ESI-MS: 214 [M−H]⁺ (100)

26. 4-Amino-4′-ethoxy-[1,1′-biphenyl]-2-ol hydrochloride

Bromo derivative used: 1-bromo-4-ethoxybenzene

Yield: 0.020 g (13% of the theoretical)

ESI-MS: 230 [M+H]⁺ (100)

27. 4-Amino-2′,4′-dimethoxy-[1,1′-biphenyl]-2-ol hydrochloride

Bromo derivative used: 1-bromo-2,4-dimethoxybenzene

Yield: 0.050 g (30% of the theoretical)

ESI-MS: 268 [M+Na]⁺ (100)

28. 4-Amino-2′,5′-dimethoxy-[1,1′]-2-biphenyl]-2-ol hydrochloride

Bromo derivative used: 2-bromo-1,4-dimethoxybenzene

Yield: 0.061 g (36% of the theoretical)

ESI-MS: 268 [M+Na]⁺ (100)

29. 5-Amino-2-(1,3-benzodioxo-5-yl)phenol hydrochloride

Bromo derivative used: 5-bromo-1,3-benzodioxol

Yield: 0.030 g (19% of the theoretical)

ESI-MS: 230 [M+H]⁺ (100)

¹H-NMR (300 MHz DMSO): δ=10.10 (s, br, 1H, OH)); 7.28 (d, J=8.2, 1H,H3); 7.09 (s, 1H, H4′); 6.96 (m, 2H, H6′ and H7′); 6.91 (s, 1H, H6);6.77 (d, J=8.2, 1H, H4); 6.04 (s, 2H, CH₂O); 3.50 (s, br, 3H, NH₃ ⁺).

30. 4-Amino-4′-methoxy-2′-methyl-[1,1′-biphenyl]-2-ol hydrochloride

Bromo derivative used: 1-bromo-4-methoxy-2-methylbenzene

Yield: 0.016 g (10% of the theoretical)

ESI-MS: 230 [M+H]⁺ (100)

31. 4-Amino-4′-phenoxy-[1,1′-biphenyl]-2-ol hydrochloride

Bromo derivative used: 1-bromo-4-phenoxybenzene

Yield: 0.024 g (13% of the theoretical)

ESI-MS: 276 [M−H]⁺ (100)

32. 4-Amino-[1,1′-biphenyl]-2,4′-diol hydrochloride

Bromo derivative used: 4-bromophenol

Yield: 0.033 g (23% of the theoretical)

ESI-MS: 200 [M−H]⁺ (100)

33. 4-Amino-2′-methyl-[1,1′-biphenyl]-2,4′-diol hydrochloride

Bromo derivative used: 4-bromo-3-methylphenol

Yield: 0.012 g (8% of the theoretical)

ESI-MS: 216 [M+H]⁺ (100)

34. 3′,4-Diamino-[1,1′-biphenyl]-2-ol hydrochloride

Bromo derivative used: 3-bromoaniline

Yield: 0.032 g (23% of the theoretical)

ESI-MS: 199 [M−H]⁺ (100)

35. 1-(4′-Amino-2′-hydroxy-1,1′-biphenyl-4-yl)ethanone hydrochloride

Bromo derivative used: 4-bromoacetophenone

Yield: 0.016 g (10% of the theoretical)

ESI-MS: 250 [M+Na]⁺ (100)

36. 4-Amino-1,1′:3′,1″-terphenyl-2-ol hydrochloride

Bromo derivative used: 3-bromo-1,1′-biphenyl

Yield: 0.050 g (28% of the theoretical)

ESI-MS: 260 [M−H]⁺ (100)

37. 5-Amino-2-(3-pyridinyl)phenol hydrochloride

Bromo derivative used: 3-bromopyridine

Yield: 0.067 g (50% of the theoretical)

ESI-MS: 187 [M+H]⁺ (100)

¹H-NMR (300 MHz, DMSO): δ=10.88 (s, br, 1H, OH); 9.09 (s, 1H, H2′); 8.81(d, J=5.5, 1H, H4′); 8.76 (d, J=8.2, 1H, H6′); 8.09 (dd, J=5.5, J=8.2,1H, H5′); 7.54 (d, J=8.3, 1H, H3); 7.02 (d, J=1.7, 1H, H6); 6.84 (dd,J=1.7, J=8.3, 1H, H4); 4.2 (s, br, 3H, NH₃ ⁺).

38. 5-Amino-2-(2-pyridinyl)phenol hydrochloride

Bromo derivative used: 2-bromopyridine

Yield: 0.038 g (28% of the theoretical)

ESI-MS: 187 [M+H]⁺ (100)

39. 5-Amino-2-(3-methyl-2-pyridinyl)phenol hydrochloride

Bromo derivative used: 2-bromo-3-methylpyridine

Yield: 0.039 g (27% of the theoretical)

ESI-MS: 201 [M+H]⁺ (100)

40. 5-Amino-2-(4-methyl-2-pyridinyl)phenol hydrochloride

Bromo derivative used: 2-bromo-4-methylpyridine

Yield: 0.057 g (39% of the theoretical)

ESI-MS: 201 [M+H]⁺ (100)

41. 5-Amino-2-(5-methyl-2-pyridinyl)phenol hydrochloride

Bromo derivative used: 2-bromo-5-methylpyridine

Yield: 0.051 g (35% of the theoretical)

ESI-MS: 201 [M+H]⁺ (100)

42. 5-Amino-2-(6-methyl-2-pyridinyl)phenol hydrochloride

Bromo derivative used: 2-bromo-6-methylpyridine

Yield: 0.056 g (39% of the theoretical)

ESI-MS: 201 [M+H]⁺ (100)

43. 5-Amino-2-(5-nitro-2-pyridinyl)phenol hydrochloride

Bromo derivative used: 2-bromo-5-nitropyridine

Yield: 0.060 g (37% of the theoretical)

ESI-MS: 230 [M−H]⁺ (100)

44. 5-Amino-2-(5-bromo-3-pyridinyl)phenyl hydrochloride

Bromo derivative used: 3,5-dibromopyridine

Yield: 0.047 g (26% of the theoretical)

ESI-MS: 265 [M]⁺ (100)

¹H-NMR (300 MHz, DMSO): δ=10.54 (s, br, 1H, OH); 8.75 (s, 1H, H2′); 8.67(s, 1H, H6′); 8.24 (s, 1H, H4′); 7.54 (d, J=8.2, 1H, H3); 6.97 (s, 1H,H6); 6.82 (d, J=8.2 1H, H4).

45. 5-Amino-2-(5-pyrimidinyl)phenol hydrochloride

Bromo derivative used: 5-bromopyrimidine

Yield: 0.067 g (50% of the theoretical)

ESI-MS: 188 [M+H]⁺ (100)

¹H-NMR (300 MHz, DMSO): δ=10.74 (s, br, 1H, OH); 9.14 (s, 1H, H2′); 9.00(s, 2H, H4′ and H6′); 7.52 (d, J=8.1, 1H, H3); 7.10 (d, J=1.6, 1H, H6);6.93 (dd, J=1.6, J=8.1, 1H, H4);3.76 (s, br, 3H, NH₃ ⁺).

Examples 46 to 90 Hair Colorants

Hair colorant solutions of the following composition were prepared:

1.25 mmol of the substance of formula (I) as per Table 1 1.25 mmol ofthe developer as per Table 1 10.0 g of lauryl ether sulfate (28% aqueoussolution) 9.0 g of ammonia (22% aqueous solution) 7.8 g of ethanol 0.3 gof ascorbic acid 0.3 g of disodium ethylenediaminetetraacetate hydrateto 100.0 g water, demineralized

Just before use, 10 g of the above colorant solution was mixed with 10 gof a 6% hydrogen peroxide solution. The mixture was then applied tobleached hair. After an exposure time of 30 minutes at 40° C., the hairwas rinsed with water, washed with a commercial shampoo and dried. Table1 summarizes the resulting colorations.

Developer III II 4,5-diamino- IV I 2,5-diamino- 1-(2′-hydroxy- 4-amino-Coupler of 2,5-diamino- phenylethanol ethyl)pyrazole 3-methyl- ExampleFormula (I) toluene sulfate sulfate sulfate phenol 46 as per violetviolet purple light Example 1 pink 47 as per violet violet purple lightExample 2 pink 48 as per dark- dark- purple light Example 3 violetviolet pink 49 as per ash- ash- bright beige Example 4 blond blond red50 as per light light gray- bright beige Example 5 gray-violet violetred 51 as per violet violet bright beige Example 6 red 52 as per violetviolet bright light Example 7 red pink 53 as per violet violet purplelight Example 8 pink 54 as per gray gray bright beige Example 9 red 55as per violet violet purple light Example 10 pink 56 as per violetviolet purple light Example 11 pink 57 as per gray- gray- purple beigeExample 12 violet violet 58 as per gray- gray- bright beige Example 13violet violet red 59 as per violet violet bright beige Example 14 red 60as per blue- blue- strawberry light Example 15 violet violet red pink 61as per light- light- bright beige Example 16 violet violet red 62 as perlight light bright beige Example 16 violet violet red 63 as per bluishbluish strawberry light Example 18 violet violet red pink 64 as perdark- dark-blue strawberry light Example 19 blue violet violet red pink65 as per dark- dark-blue strawberry light Example 20 blue violet violetred pink 66 as per ash- ash- bright beige Example 21 blond blond red 67as per bluish bluish strawberry light Example 22 violet violet red pink68 as per violet violet bright beige Example 23 red 69 as per dark darkpurple light Example 24 violet violet pink 70 as per violet violetbright beige Example 25 red 71 as per light- light- bright beige Example26 violet violet 72 as per light light gray- bright beige Example 27gray-violet violet red 73 as per ash- ash- bright beige Example 28 blondblond red 74 as per violet violet purple light Example 29 pink 75 as perlight light bright beige Example 30 violet violet red 76 as per light-light- bright beige Example 31 violet violet red 77 as per dark- dark-purple light Example 32 violet violet pink 78 as per light- light-bright beige Example 33 violet violet red 79 as per dark dark purplelight Example 34 violet violet pink 80 as per light- light-bluelight-straw- light Example 35 blue violet violet berry red pink 81 asper light- light- bright beige Example 36 violet violet red 82 as perdark dark strawberry beige Example 37 blue blue red pink 83 as per ash-ash- bright beige Example 38 blond blond red 84 as per ash- ash- brightbeige Example 39 blond blond red 85 as per ash- ash- bright beigeExample 40 blond blond red 86 as per gray gray bright beige Example 41red 87 as per gray gray bright beige Example 42 red 88 as per light-light- bright yellow Example 43 blond blond red 89 as per dark darkstrawberry light Example 44 blue blue red pink 90 as per dark darkstrawberry light Example 45 blue blue red pink

Examples 91 to 114 Hair Colorants

Hair colorant solutions of the following composition were prepared:

X g of 3-aminophenol derivative of formula (I) (coupler K1 to K4 as perTable 4) U g of developer E8 to E15 as per Table 2 Y g of coupler K12 toK36 as per Table 4 10.0 g of lauryl ether sulfate (28% aqueous solution)9.0 g of ammonia (22% aqueous solution) 7.8 g of ethanol 0.3 g ofascorbic acid 0.3 g of disodium ethylenediaminetetraacetate hydrate to100.0 g water, demineralized

Just before use, 30 g of the above colorant solution was mixed with 30 gof a 6% aqueous hydrogen peroxide solution. The mixture was then appliedto bleached hair. After an exposure time of 30 minutes at 40° C., thehair was rinsed with water, washed with a commercial shampoo and dried.Table 5 summarizes the resulting colorations.

TABLE 2 Developers E8 1,4-diaminobenzene E9 2,5-diaminophenylethanolsulfate E10 3-methyl-4-aminophenol E11 4-amino-2-aminomethylphenoldihydrochloride E13 N,N-bis-(2′-hydroxyethyl)-p-phenylenediamine sulfateE14 4,5-diamino-1-(2′-hydroxyethyl)pyrazole sulfate E152,5-diaminotoluene sulfate

TABLE 3 Direct Dyes D2 6-chloro-2-ethylamino-4-nitrophenol D32-amino-6-chloro-4-nitrophenol

TABLE 4 Couplers K1 4-amino-3′-methyl-[1,1′-biphenyl]-2-ol K24-amino-4′-methyl-3′-nitro-[1,1′-biphenyl]-2-ol K35-amino-2-(3-pyridinyl)phenol K4 5-amino-2-(5-pyrimidinyl)phenol K122-amino-4-(2′-hydroxyethyl)aminoanisole sulfate K131,3-diamino-4-(2′-hydroxyethoxy)benzene sulfate K142,4-diamino-5-fluorotoluene sulfate K18 N-(3-dimethylamino)phenylureaK19 1,3-bis-(2,4-diaminophenoxy)propane tetrahydrochloride K213-aminophenol K22 5-amino-2-methylphenol K233-amino-2-chloro-6-methylphenol K24 5-amino-4-fluoro-2-methylphenolsulfate K25 1-naphthol K31 1,3-dihydroxybenzene K322-methyl-1,3-dihydroxybenzene K33 1-chloro-2,4-dihydroxybenzene K344-(2′-hydroxyethyl)amino-1,2-methylenedioxy- benzene hydrochloride K362-amino-5-methylphenol

TABLE 5 Hair Colorants Example No. 91 92 93 94 95 96 Dyes (Dye quantityin grams) K1 0.10 0.12 0.05 0.07 0.10 0.12 E8 0.30 E9 0.25 0.20 E10 0.10E15 0.25 0.30 0.25 K12 0.05 K13 0.05 K21 0.05 K22 0.05 K23 0.05 0.100.10 0.10 K25 0.10 K31 0.20 0.15 0.10 0.10 K32 0.20 0.10 K33 0.20 K360.10 Coloring result blond blond blond blond blond blond Example No. 9798 99 100 101 102 Dyes (Dye quantity in grams) K2 0.10 0.12 0.05 0.070.10 0.12 E8 0.30 E9 0.25 0.20 E10 0.10 E15 0.25 0.30 0.25 K12 0.05 K130.05 K21 0.05 K22 0.05 K23 0.05 0.10 0.10 0.10 K25 0.10 K31 0.20 0.150.10 0.10 K32 0.20 0.10 K33 0.20 K36 0.10 Coloring result blond blondblond blond blond blond Example No. 103 104 105 106 107 108 Dyes (Dyequantity in grams) K3 0.10 0.12 0.05 0.07 0.10 0.12 E8 0.30 E9 0.25 0.20E10 0.10 E15 0.25 0.30 0.25 K12 0.05 K13 0.05 K21 0.05 K22 0.05 K23 0.050.10 0.10 0.10 K25 0.10 K31 0.20 0.15 0.10 0.10 K32 0.20 0.10 K33 0.20K36 0.10 Coloring result blond blond blond blond blond blond Example No.109 110 111 112 113 114 Dyes (Dye quantity in grams) K4 0.10 0.12 0.050.07 0.10 0.12 E8 0.30 E9 0.25 0.20 E10 0.10 E15 0.25 0.30 0.25 K12 0.05K13 0.05 K21 0.05 K22 0.05 K23 0.05 0.10 0.10 0.10 K25 0.10 K31 0.200.15 0.10 0.10 K32 0.20 0.10 K33 0.20 K36 0.10 Coloring result blondblond blond blond blond blond

Examples 115 to 138 Hair Colorants

Hair colorant solutions of the following composition were prepared:

X g of 3-aminophenol derivative of formula (I) (coupler K1 to K4 as perTable 4) U g of developer E8 to E15 as per Table 2 Y g of coupler K11 toK36 as per Table 4 Z g of direct dye D2 and/or D3 as per Table 3 10.0 gof lauryl ether sulfate (28% aqueous solution) 9.0 g of ammonia (22%aqueous solution) 7.8 g of ethanol 0.3 g of ascorbic acid 0.3 g ofdisodium ethylenediaminetetraacetate hydrate to 100.0 g water,demineralized

Just before use, 30 g of the above colorant cream was mixed with 30 g ofa 6% aqueous hydrogen peroxide solution. The mixture was then applied tohair. After an exposure time of 30 minutes at 40° C., the hair wasrinsed with water, washed with a commercial shampoo and dried. Table 6summarizes the resulting colorations.

TABLE 6 Hair Colorants Example No. 115 116 117 118 119 120 Dyes (Dyequantity in grams) K1 0.60 1.30 1.15 0.15 0.15 0.15 E8 1.50 E11 0.10 E131.60 0.70 E14 0.10 0.10 E15 1.80 0.70 0.70 K12 0.50 K14 0.10 K18 0.05K19 0.10 K23 0.05 0.10 0.10 0.10 K24 0.15 K31 0.90 1.10 1.10 0.40 0.400.40 K34 0.10 D2 0.10 0.10 0.10 D3 0.05 0.05 0.05 Coloring result blackblack black brown brown brown Example No. 121 122 123 124 125 126 Dyes(Dye quantity in grams) K2 0.60 1.30 1.15 0.15 0.15 0.15 E8 1.50 E110.10 E13 1.60 0.70 E14 0.10 0.10 E15 1.80 0.70 0.70 K12 0.50 K14 0.10K18 0.05 K23 0.05 0.10 0.10 0.10 K24 0.15 K31 0.90 1.10 1.10 0.40 0.400.40 K34 0.10 D2 0.10 0.10 0.10 D3 0.05 0.05 0.05 Coloring result blackblack black brown brown brown Example No. 127 128 129 130 131 132 Dyes(Dye quantity in grams) K3 0.60 1.30 1.15 0.15 0.15 0.15 E8 1.50 E110.10 E13 1.60 0.70 E14 0.10 0.10 E15 1.80 0.70 0.70 K12 0.50 K14 0.10K18 0.05 K23 0.05 0.10 0.10 0.10 K24 0.15 K31 0.90 1.10 1.10 0.40 0.400.40 K34 0.10 D2 0.10 0.10 0.10 D3 0.05 0.05 005 Coloring result blackblack black brown brown brown Example No. 133 134 135 136 137 138 Dyes(Dye quantity in grams) K4 0.60 1.30 1.15 0.15 0.15 0.15 E8 1.50 E110.10 E13 1.60 0.70 E14 0.10 0.10 E15 1.80 0.70 0.70 K12 0.50 K14 0.10K18 0.05 K23 0.05 0.10 0.10 0.10 K24 0.15 K31 0.90 1.10 1.10 0.40 0.400.40 K34 0.10 D2 0.10 0.10 0.10 D3 0.05 0.05 0.05 Coloring result blackblack black brown brown brown

Unless otherwise indicated, the percentages given in the present patentapplication are by weight.

1. Agent for dyeing keratin fibers based on a developer-couplercombination and characterized in that it contains at least one3-aminophenol derivative of formula (I) or a physiologically compatible,water-soluble salt thereof

wherein R1 denotes a group of formula (II) or (III)

wherein R2, R3, R4, R5 and R6 independently of each other denotehydrogen, a halogen atom, a cyano group, hydroxyl group, (C₁–C₄)-alkoxygroup, a phenoxy group, a (C₁–C₄)-hydroxyalkoxy group, a (C₁–C₆)-alkylgroup, a phenyl group, a (C₁–C₄)-alkyl thioether group, a mercaptogroup, a nitro group, an amino group, a (C₁–C₄)-alkylamino group, ahydroxy(C₂–C₄)alkylamino group, a di(C₁–C₄)alkylamino group, adi[hydroxy(C₂–C₄)alkyl]amino group, a [dihydroxy (C₃–C₄)alkyl]-aminogroup, a [hydroxy(C₂–C₄)alkyl]-(C₁–C₄)-alkylamino group, atrifluoromethyl group, a —C(O)H group, a —C(O)CH₃ group, a —C(O)CF₃group, a —Si(CH₃)₃ group, a (C₁–C₄)-hydroxyalkyl group, a(C₂–C₄)-dihydroxyalkyl group, a (C₁–C₄)-ami-noalkyl group or a(C₁–C₄)-cyanoalkylgroup, or two adjacent R2 to R6 groups form an—O—CH₂—O-bridge; X₁, X₂, X₃, X₄ and X₅ independently of each otherdenote nitrogen or a C—R7 group, C—R8 group, C—R9 group, C—R10 group orC—R11 group, provided that at least one and at the most three of the X₁to X₅ groups denote nitrogen; and R7, R8, R9, R10 and R11 independentlyof each other denote hydrogen, a halogen atom, a cyano group, a(C₁–C₆)-alkyl group, a (C₁–C₄)-alkyl thioether group, a mercapto group,a nitro group, an amino group a (C₁–C₄)-alkylamino group, adi(C₁–C₄)alkylamino group, a trifluoromethyl group, a —C(O)H group, a—C(O)CH₃ group, a —C(O)CF₃ group, a —Si(CH₃)₃ group, a —C(O)—NH₂ group,a (C₁–C₄)-hydroxyalkyl group or a (C₂–C₄)-dihydroxyalkyl group.
 2. Agentaccording to claim 1, characterized in that for the compounds of formula(I) (i) R1 stands for a group of formula (II) with R2 and R6 denotinghydrogen, or (ii) R1 stands for a group of formula (I) with X₁ and X₅denoting C—R7 and C—R11, with R7 and R11 denoting hydrogen.
 3. Agentaccording to claim 1 or 2, characterized in that the compounds offormula (I) are selected from among4-amino-3′-methyl-[1,1′-biphenyl]-2-ol,4-amino-4′-methyl-3′-nitro-[1,1′-biphenyl]-2-ol,4-amino-[1,1′-biphenyl]-2,4′-diol, 5-amino-2-(3-pyridinyl)phenol and5-amino-2-(5-pyrimidinyl)phenol as well as the physiologicallycompatible, water-soluble salts thereof.
 4. Agent according to one ofclaims 1 to 3, characterized in that it contains the 3-aminophenolderivative of formula (I) in an amount from 0.005 to 20 weight percent.5. Agent according to one of claims 1 to 4, characterized in that thedeveloper is selected from the group consisting of 1,4-diaminobenzene,1,4-diamino-2-methylbenzene, 1,4-diamino-2,6-dimethylbenzene,1,4-diamino-3,5-diethylbenzene, 1,4-diamino-2,5-dimethylbenzene,1,4-diamino-2,3-dimethylbenzene, 2-chloro-1,4-diaminobenzene,1,4-diamino-2-(thiophen-2-yl)benzene,1,4-diamino-2-(thiophen-3-yl)benzene,1,4-diamino-2-(pyridin-3-yl)benzene, 2,5-diaminobiphenyl,1,4-diamino-2-methoxymethylbenzene, 1,4-diamino-2-aminomethylbenzene,1,4-diamino-2-hydroxymethylbenzene,1,4-diamino-2-(2-hydroxyethoxy)benzene,2-[2-(acetylamino)ethoxy]-1,4-diaminobenzene, 4-phenylaminoaniline,4-dimethylaminoaniline, 4-diethylaminoaniline, 4-dipropylaminoaniline,4-[ethyl-(2-hydroxyethyl)amino]aniline,4-[di(2-hydroxyethyl)amino]aniline,4-[di(2-hydroxyethyl)amino]-2-methylaniline,4-[(2-methoxy-ethyl)amino]aniline, 4-[(3-hydroxypropyl)amino]aniline,4-[(2,3-dihydroxypropyl)amino]aniline,1,4-diamino-2-(1-hydroxyethyl)benzene,1,4-diamino-2-(2-hydroxyethyl)benzene,1,4-diamino-2-(1-methylethyl)benzene,1,3-bis-[(4-aminophenyl)(2-hydroxyethyl)amino]-2-propanol,1,4-bis-[(4-aminophenyl)amino]butane,1,8-bis-(2,5-diaminophenoxy)-3,6-dioxaoctane, 4-aminophenol,4-amino-3-methylphenol, 4-amino-3-(hydroxymethyl)phenol,4-amino-3-fluorophenol, 4-methylaminophenol,4-amino-2-(aminomethyl)phenol, 4-amino-2-(hydroxymethyl)phenol,4-amino-2-fluoro-phenol, 4-amino-2-[(2-hydroxyethyl)amino]-methylphenol,4-amino-2-methylphenol, 4-amino-2-(methoxymethyl)phenol,4-amino-2-(2-hydroxyethyl)phenol, 5-aminosalicylic acid,2,5-diaminopyridine, 2,4,5,6-tetraminopyrimidine,2,5,6-triamino-4-(1H)-pyrimidone,4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazole,4,5-diamino-1-(1-methylethyl)-1H-pyrazole,4,5-diamino-1-[(4-methylphenyl)methyl]-1H-pyrazole,1-[(4-chlorophenyl)methyl]-4,5-diamino-1H-pyrazole,4,5-diamino-1-methyl-1H-pyrazole, 2-aminophenol, 2-amino-6-methylphenol,2-amino-5-methylphenol and 1,2,4-trihydroxybenzene.
 6. Agent accordingto one of claims 1 to 5, characterized in that besides the compounds offormula (I) it contains at least one additional known coupler selectedfrom the group consisting of N-(3-dimethylaminophenyl)urea,2,6-diaminopyridine, 2-amino-4-[(2-hydroxyethyl)amino]anisole,2,4-diamino-1-fluoro-5-methylbenzene,2,4-diamino-1-methoxy-5-methylbenzene,2,4-diamino-1-ethoxy-5-methylbenzene,2,4-diamino-1-(2-hydroxyethoxy)-5-methylbenzene,2,4-di[(2-hydroxyethyl)amino]-1,5-dimethoxybenzene,2,3-diamino-6-methoxypyridine,3-amino-6-methoxy-2-(methylamino)pyridine,2,6-diamino-3,5-dimethoxypyridine, 3,5-diamino-2,6-dimethoxypyridine,1,3-diaminobenzene, 2,4-diamino-1-(2-hydroxyethoxy)benzene,1,3-diamino-4-(2,3-dihydroxypropoxy)benzene,1,3-diamino-4-(3-hydroxypropoxy)benzene,1,3-diamino-4-(2-methoxyethoxy)benzene,2,4-diamino-1,5-di(2-hydroxyethoxy)benzene,1-(2-aminoethoxy)-2,4-diaminobenzene,2-amino-1-(2-hydroxyethoxy)-4-methylaminobenzene,2,4-diaminophenoxyacetic acid, 3-[di(2-hydroxy-2-ethyl)amino]aniline,4-amino-2-di[(2-hydroxyethyl)amino]-1-ethoxybenzene,5-methyl-2-(1-methylethyl)phenol, 3-[(2-hydroxyethyl)amino]aniline,3-[(2-aminoethyl)amino]aniline, 1,3-di(2,4-diaminophenoxy)propane,di(2,4-diaminophenoxy)methane, 1,3-diamino-2,4-dimethoxybenzene,2,6-bis-(2-hydroxyethyl)aminotoluene, 4-hydroxyindole,3-dimethylaminophenol, 3-diethylaminophenol, 5-amino-2-methylphenol,5-amino-4-fluoro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol,5-amino-4-ethoxy-2-methylphenol, 3-amino-2,4-dichlorophenol,5-amino-2,4-dichloropheno3-amino-2-methylphenol,3-amino-2-chloro-6-methylphenol, 3-aminophenol,2-[(3-hydroxyphenyl)amino]acetamide,5-[(2-hydroxyethyl)amino]-4-methoxy-2-methylphenol,5-[(2-hydroxyethyl)amino]-2-methylphenol,3-[(2-hydroxyethyl)amino]phenol, 3-[(2-methoxyethyl)amino]phenol,5-amino-2-ethylphenol, 5-amino-2-methoxyphenol,2-(4-amino-2-hydroxyphenoxy)ethanol,5-[(3-hydroxypropyl)amino]-2-methylphenol,3-[(2,3-dihydroxypropyl)-amino]-2-methylphenol,3-[(2-hydroxyethyl)amino]-2-methylphenol, 2-amino-3-hydroxypyridine,2,6-dihydroxy-3,4-dimethylpyridine, 5-amino-4-chloro-2-methylphenol,1-naphthol, 2-methyl-1-naphthol, 1,5-dihydroxynaphthalene,1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene,2,7-dihydroxynaphthalene, 2-methyl-1-naphthol acetate,1,3-dihydroxybenzene, 1-chloro-2,4-dihydroxybenzene,2-chloro-1,3-dihydroxybenzene,1,2-dichloro-3,5-dihydroxy-4-methylbenzene,1,5-dichloro-2,4-dihydroxybenzene1,3-dihydroxy-2-methylbenzene,3,4-methylenedioxyphenol, 3,4-methylenedioxyaniline,5-[(2-hydroxyethyl)amino]-1,3-benzodioxole,6-bromo-1-hydroxy-3,4-methylenedioxybenzene, 3,4-diaminobenzoic acid,3,4-dihydro-6-hydroxy-1,4(2H)benzoxazine,6-amino-3,4-dihydro-1,4(2H)benzoxazine, 3-methyl-1-phenyl-5-pyrazolone,5,6-dihydroxyindole, 5,6-dihydroxyindoline, 5-hydroxyindole,6-hydroxyindole, 7-hydroxyindole and 2,3-indolinedione.
 7. Agentaccording to one of claims 1 to 6, characterized in that, based on thetotal amount of colorant, it contains the developers and couplers in atotal amount of 0.005 to 20 weight percent, each.
 8. Agent according toone of claims 1 to 7, characterized in that it contains additionally atleast one direct dye.
 9. Agent according to one of claims 1 to 8,characterized in that it has a pH from 6.5 to 11.5.
 10. Ready-to-useagent for oxidative dyeing of keratin fibers which, in a mediumappropriate for dyeing, contains at least one developer, at least onecoupler and at least one oxidant, characterized in that it contains asthe coupler at least one 3-aminophenol derivative of formula (I)according to one of claims 1 to
 3. 11. Agent according to one of claims1 to 10, characterized in that it is a hair colorant.
 12. 3-Aminophenolderivative of formula (I) or a physiologically compatible, water-solublesalt thereof

wherein R1 denotes a group of formula (II) or (III)

wherein R2, R3, R4, R5 and R6 independently of each other denotehydrogen, a halogen atom, a cyano group, hydroxyl group, (C₁–C₄)-alkoxygroup, a phenoxy group, a (C₁–C₄)-hydroxyalkoxy group, a (C₁–C₆)-alkylgroup, a phenyl group, a (C₁–C₄)-alkyl thioether group, a mercaptogroup, a nitro group, an amino group, a (C₁–C₄)-alkylaMino group, ahydroxy-(C₂–C₄)-alkylamino group, a di(C₁–C₄)-alkylamino group, adi[hydroxy-(C₂–C₄)-alkyl]amino group, a [dihydroxy-(C₃–C₄)alkyl]aminogroup, a [hydroxy-(C₂–C₄)-alkyl]-(C₁–C₄)-alkylamino group, atrifluoromethyl group, a —C(O)H group, a —C(O)CH₃ group, a —C(O)CF₃group, a —Si(CH₃)₃ group, a (C₁–C₄)-hydroxyalkyl group, a(C₂–C₄)-dihydroxyalkyl group, a (C₁–C₄)-aminoalkyl group or a(C₁–C₄)-cyanoalkylgroup, or two adjacent R2 to R6 groups form an—O—CH₂—O— bridge; X₁, X₂, X₃, X₄ and X₅ independently of each otherdenote nitrogen of a C—R7 group, C—R8 group, C—R9 group, C—R10 group orC—R11 group, provided that at least one and at the most three of the X₁to X₅ groups denote nitrogen; and R7, R8, R9, R10 and R11 independentlyof each other denote hydrogen, a halogen atom, a cyano group, a(C₁–C₆)-alkyl group, a (C₁–C₄)-alkyl thioether group, a mercapto group,a nitro group, an amino group, a (C₁–C₄)-alkylamino group, adi(C₁–C₄)-alkylamino group, a trifluoromethyl group, a —C(O)H group, a—C(O)CH₃ group, a —C(O)CF₃ group, a —Si(CH₃)₃ group, a —C(O)—NH₂ group,a (C₁–C₄)-hydroxyalkyl group or a (C₂–C₄)-dihydroxyalkyl group,providing that (i) R1 is not a 2-pyridyl group and (ii) R1 is not a2-hydroxy-4-aminophenyl group.